Benzimidazole compound, method of use, and compositions

ABSTRACT

5,6-Dichloro-1-phenoxycarbonyl-2-trifluoromethyl-benzimidazole finds particular use as an acaricide.

Unlted States .Paten 91 [111 3,725,554 Burton et al. 1 Apr. 3, 1973 [s41 BENZIMIDAZOLE COMPOUND, 52 us. CI ..424/273 METHOD OF USE, AND [51] Int. Cl. ..A0ln 9/22 COMPOSITIONS [58] Field of Search ..424/274 [75] Inventors: Dennis Ernest Burton; Geoffrey Tat- [56] Reiernces Cited tersall Newbold, both of Saffron Walden; Albert Percival, l-lauxton; OTHER PUBLICATIONS Alan James Lambie, Kidderminster; Ian Robert Semis], y a" of (Glrgzgdl et al., J. Org. Chem., Vol. 27, p- 227-229 England 4 Morgan, J. Chem. So c. (London) 1961, v p. [73] Assignee: Fisqns Limited, London, England 2,344-2,345.

[22] Filed: 1971 Primary ExaminerStanley J. Friedman [21] Appl. No.: 199,018 Attorney-E. F. Wenderoth et al.

Related US. Application Data 57 ABSTRACT Division Of ,1 P'" 17, 1957', which 5,6-Dichloro-l-phenoxycarbonyl-Z-trifluoromethylis a continuation-in-part of Ser. No. 457,519, May 20, 1965, abandoned.

benzimidazole finds particular use as an acaricide.

5 Claims, No Drawings tive composition which BENZIMIDAZOLE COMPOUND, METHOD OF USE, AND COMPOSITIONS This application is a division of application Ser. No. 631,175, filed Apr. 17, 1967 which application is a continuation-in-part application of application Ser. No. 457,519 filed May 20, 1965 and now abandoned.

The present invention relates to certain substituted benzimidazoles which have been found to possess physiological activity, to their preparation and to agricultural chemical and related compositions containing the same.

It has been found that the substituted benzimidazoles as hereinafter described are active as pesticides in many fields and that certain members are highly active as herbicides, aearicides, insecticides, molluscicides, fungicides and bactericides.

Accordingly the present invention is for a physiologically active composition which contains as an active ingredient a substituted benzimidazole of the following formula:

wherein the above formula R, R, R and R may be the same or different and are selected from the group comprising hydrogen, alkyl (for example of 1-6 carbon atoms such as methyl, ethyl or propyl), hydroxy, alkoxy (for example methoxy, ethoxy, or butoxy), nitro, halogen (for example chloro, bromo or fluoro), pseudo-halogen (for example cyano, thiocyano, isothiocyano or azido), substituted alkyl (for example trifluoromethyl, chloromethyl, bromomethyl, trichloromethyl, hydroxymethyl, 2-chloroethyl, 2- hydroxyethyl or Z-methoxyethyl), carboxy, carboxy ester, carboxy amide, N-substituted carboxy amide, N- disubstituted carboxy amide, amino or mono or disubstituted amino (for example methylamino dimethylamino acetylamino, trifluoroacetylamino, benzenesulphomamido, paratoluenesulphonamido, methanesulphonamido) thiol, alkylthiol and oxygenated derivatives thereof (for example SOR or --S0,R where R is alkyl) sulphonic acid and esters and amides thereof and substituted amides (for example phenylsulphamyl, ethylsulphamyl, chloroethylsulphamyl) and a heterocyclic ring attached to the benzimidazole system through a nitrogen atom (for example morpholine, pyridine, piperidine, piperazine, N'- alkyl or N'-aryl piperazine), radicals, where X is trifluoromethyl or pentafluoroethyl, and where R is alkyl (for example methyl, ethyl hexyl, decyl or dodecyl), substituted alkyl (for example chloromethyl or bromoethyl), aryl (for example phenyl or naphthyl), substituted aryl (for example tolyl or xylyl), cycloalkyl or substituted cycloalkyl. I

The present invention is also for a physiologically accontains a substituted benzimidazole as identified above and at least one material selected from the group comprising wetting agents, inert diluents and solvents.

The present invention is also for a composition suitable for use as a molluscicide which comprises the substituted benzimidazole as identified above admixed with appropriate carriers. Appropriate carriers include solid diluents, edible substances attractive to molluscs and paints, for example suitable for marine application.

The present invention is also for the treatment of plants, materials, the soil, land or aquatic areas, which comprises applying thereon or thereto a physiologically active composition as defined above. The materials treated according to the invention may be any material susceptible to attack be detrimental organisms such as fabric, paper and wood. v

The present invention also comprises the new substituted benzimidazoles of the formula:

wherein the above formula, the groups R, R R", R, R" and X have the significance indicated, above.

It has been found that the substituted benzimidazoles according to the invention generally possess physiologi- According to a preferred embodiment, the present invention is for compounds of the formula:

wherein R, R, R, R and R have the significance indicated above but where at least one of the'groups R, R, R and R is chlorine, bromine, iodine, fluorine,

nitro, amino alkyl or trifluoromethyl, suitably also ,6-dichlorol -ethoxycarbonyl-2-trifluorom ethylbenzimidazole,. 5,6-dichloro-l-methoxycarbonyl-2-trifluoromethylbenzimidazole, 6-chloro-4-nitro-l-ethoxycarbonyl-2- trifluoromethylbenzimidazole,

4-chloro-6-iodol -ethoxycarbonyl-2- trifluoromethylbenzimidazole,

5 ,6-dichlorol -cyclohexyloxycarbonyl-2- trifluoromethylbenzimidazole,

6-bromo-4,5-dichlorol -(2 '-chloroethoxycarbonyl Z-trifluoromethyl-benzimidazole, 4,5 -dichloro-l -methoxycarbonyl-2-trifluoromethylbenzimidazole, 4,5-dichloro-1-cyclohexyloxycarbonyl-Z- trifluoromethylbenzimidazole, 4,5 ,6-trichlorol -cyclohexyloxycarbonyl-2- trifluoromethylbenzimidazole, 4,5-dichloro-l-hexyloxycarbonyl-2-trifluoromethylbenzimidazole,

4,5 ,6-trichlorol -alphanaphthyloxycarbonyl-2- trifluoromethylbenzimidazole, 4,6-dichloro-1-phenoxycarbonyl-Z-trifluoromethylbenzimidazole,

4-bromo-5 ,6-dichlorol -ethoxycarbonyl-2- trifluoromethylbenzimidazole,

4-bromo-5 ,6-dichlorol -pentyloxycarbonyl-2- trifluoromethylbenzimidazole, 4-bromo-5,6-dichloro-l-propyloxycarbonyl-2- trifluoromethylbenzimidazole,

6-chloro-4-nitrol -decyloxycarbonyl-2-trilfuoromethylbenzimidazole, 6-chloro-4-nitro-l-isopropoxycarbonyl-2- trifluoromethylbenzimidazole,

4,5 -dichlorol -ethoxycarbonyl-2-trifluoromethylbenzimidazole,

4,5 -dichlorol -isopropoxycarbonyl-2- trifluoromethylbenzimidazole, S-nitro-l-isopropoxycarbonyl-2-trifluoromethylbenzimidazole, 4,6-dibromo-l-ethoxycarbonyl-2-trifluoromethylbenzimidazole and 4-bromo-6-chlorol -phenoxycarbonyl-2- trifluoromethylbenzimidazole.

According to one embodiment of the invention, the substituted benzimidazoles as indicated are prepared by reacting an alkali metal salt of the corresponding benzimidazole derivative with a chloroforrnate, in accordance with the following formula:

I l /c--x m-o oo ci WP R -c -N wherein the above formula R, R, R, R, R and X have the significance indicated above and M is an alkali metal.

Alternatively the substituted benzimidazoles may be prepared by reacting the corresponding benzimidazole derivative with the appropriate chloroformate in the presence of a base, such as trimethylamine of triethylamine.

In the case of the substituted benzimidazoles bearing an amino group, these are suitably prepared by the reaction of the corresponding nitro-substituted benzimidazole. In the case of the substituted benzimidazoles bearing a nitro group, these are suitably prepared by the nitration of the corresponding subsolved emulsifying agents so as to act as a self-emulsifiable oil on addition to water.

The substituted benzimidazoles mayalso be admixed with a wetting agent with or without an inert diluent to form a wettable powder which is soluble or dispersible in water, or may be mixed with the inert diluent to form a solid or powdery product.

Inert diluents with which the substituted benzimidazolesand salts thereof may be incorporated include solid inert media comprising powdered or divided solid materials, for example, clays, sands, talc, mica, fertilizers and the like, such products either comprising dust or larger particle size materials.

The wetting agents used may comprise anionic compounds such as for example soaps, fatty sulphate esters such as dodecyl sodium sulphate, fatty aromatic sulphonates such as alkylbenzene sulphonates or butyl naphthalene sulphonate, more complex fatty sulphonates such as the amide condensation product of oleic acid and N-methyl taurine or the sodium sulphonate of dioctyl succinate.

The wetting agents may also comprise non-ionic wetting agents such as for example condensation products of fatty acids, fatty alcohols or fatty substituted phenols with ethylene oxide, or fatty esters of sugars or polyhydric alcohols, or the products obtained from the latter by condensation with ethylene oxide, or the products known as block copolymers of ethylene oxide and propylene oxide. The wetting agents may also comprise cationic agents such as for example cetyl trimethyl-ammonium bromide and the like.

For molluscicidal use the benzimidazole may for example be-made into a granule or pellet, for example of plaster of paris, which may be scattered'in an aquatic habitatof the molluscs, and from which the benzimidazole may diffuse, or dissolved into a spread Edible substances attractive to molluscs with which the benzimidazoles may be admixed include fungi, oilcake, fruit waste, luceme flour, cereals, cereal products, vegetables, vegetables products, bran, biscuits and the like. The physiologically active compositions according to the present invention may contain in addition to the substituted benzimidazole or salts thereof, other physiologically active materials such as herbicides, insecticides, fungicides and molluscides. Insecticidal compositions may contain edible substances attractive to insects such as sugar, molasses and protein hydrolysates, suitably also with specific insect attractants.

The substituted benzimidazoles find particular use as acaricides, and a special feature of the invention is their use as acaricides, and acaricidal compositions containing the same. Substituted benzimimidazoles which are of especial value as acaricides include:

5,6-dichloro-1-phenoxycarbonyl-2-trifluoromethylbenzimidazole, 4-bromo-6-chloro-1-ethoxycarbonyl-2- trifluoromethylbenzimidazole,

4,6-dibromo- 1 -isopropoxycarbonyl-2- trifluoromethylbenzimidazole,

6-bromo-4-chloro-l-ethoxycarbonyl-2- trifluoromethylbenzimidazole and 6-bromo-4,5-dichloro-l-isopropoxycarbonyl-Z- trifluoromethylbenzimidazole.

The substituted benzimidazoles may be used as acaricides in any of the conventional ways, such as the control of mites on plants, the control of mites on or in stored products of vegetable or animal origin such as grain, and the control of mites, such as ticks, on living animals.

The acaricidal compositions according to the present invention may contain in addition to the substituted benzimidazole or salts thereof, other physiologically active materials such as herbicides, insecticides, fungicides and molluscides.

The following examples are given to illustrate the present invention; the parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 Twenty-nine Grams of 4 ,5 ,6-trich1oro-2- trifluoromethylbenzimidazole were dissolved by warming in a mixture of 290 milliliters of benzene and 10 milliliters of absolute ethanol. A solution of 2.3 grams of sodium in 50 milliliters of dry ethanol was then added dropwise to the stirred warmed solution. After heating for a further 30 minutes, the solvents were removed in vacuo and the residue taken up in 200 milliliters of dry acetone. This solution was then treated with an acetone solution of 10.9 grams of ethylchloroformate and finally heated at reflux, with stirring for 1 hour. After allowing to cool, the reaction mixture was filtered to remove the deposited salt. The filtrate and acetone washings were concentrated to about 50 milliliters, when a crystalline solid separated on cooling. This solid was filtered off and recrystallized, after drying, from ligroin to give carbethoxy- 4,5,6(5,6,7-trich1oro-2-trifluoromethylbenzimidazole as a colorless product (21.5 g., 60 percent), melting point 116118C.

Analysis:

C H CI F N O requires: C, 36.54; H, 1.67; CI,

found: C, 36.50; H, 1.50; CI, 29.35; N, 7.70%

EXAMPLE 2 7.8 grams of phenyl chloroformate in 10 milliliters of dry acetone was added dropwise to a mixture of 10.4 grams of 2,5-bis-trifluoromethylbenzimidazole, 6.1 milliliters of triethylamine and milliliters of dry acetone. The temperature increased from 20 to 38 during the addition. Finally the mixture was refluxed for 1 hour. The triethylamine hydrochloride was filtered off and washed with dry acetone. The filtrate and washings were concentrated and kept at 0 for 24 hours. The crystalline material was filtered off, dried and recrystallized twice from ethanol to give 7.6 grams of white needles of l-carbophenoxy-2,5-bistrifluoromethylbenzimidazole (melting point 8486). Analysis:

C H F N O requires: C, 51.35; H, 2.16; F, 30.46;

N, 7.49% found: C, 51.50; H, 2.25; F, 30.25; N, 7.75%

Examples 3-5 3 The following compounds were prepared by analogous methods to those of Examples 1. and 2.

3. 4,5 ,6-trich1oro-1-methoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 153154C.

4. 5 ,6-dich1oro1-ethoxycarbony1-4-nitro-2- trifluoromethylbenzimidazole, melting point 113C.

5. 4 ,5 ,6-trich1orol -isopropoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 134135C.

6. 1-isopropoxycarbony1-2,5-bi s trif1uoromethy1- benzimidazole, melting point 63C. v 7. 6-chloro-1-isopropoxycarbonyl-4-nitro-2- trifluoromethylbenzimidazole, melting point 126C. 1-phenoxycarbonyl-2-trifluoromethylbenzimidazole, melting point 58C. 9. 5 -methyl-1-phenoxycarbonyl-2-trifluoromethylbenzimidazole, melting point 99-100C. 10. 4-ch1oro-1-phenoxycarbony1-2-trifluoromethy1- benzimidazole, melting point 71-72C. 1 l. 5-bromo-1-phenoxycarbonyl-2-trifluoromethylbenzimidazole, melting point 7 l72C. 12. 5-iodol -phenoxycarbonyLZ-trifluoromethylbenzimidazole, melting point l03-105C. 13. 5 ,6-dimethyl- 1 -phenoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 1 14C. 14.

trifluoromethylbenzimidazole, 103C. 15.

trifluoromethylbenzimidazole, l54-l 56C. 16. 6-chloro-4-nitrol -phenyoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 1 19-121C. l7.

trifluoromethylbenzimidazole, l38-140C.

5 ,6-dichloro-1phenoxycarbonyl-2- melting point 4-chloro-6-nitro-1-phenoxycarbonyl-2- melting point 4 ,5 ,6-trichlorol -phenoxycarbonyl-2- melting point l8. bromo-l-ethoxycarbonyl-2-trifluoromethylbenzimidazole, melting point 6365C.

l9. 4,5-dichloro-l-ethoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 109-ll0C.

20. 4,5-dichloro-l-isopropoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 21. 1-isopropoxycarbonyl-5-nitro-2-trifluoromethylbenzimidazole, melting point 7 2-74C.

22. 6-bromo-4-chloro-l-ethoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 9394C.

23. 6-bromo-4,5-dichloro-l-isopropoxycarbonyl-2- trifluoromethylbenzimidazole, melting point l30l3lC.

24. S-bromol -isopropoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 74-75C.

25. 4,6-dibromo- 1 -ethoxycarbonyl-2- trifluoromethylbenzimidazole, melting point ll2-ll4C.

26. 1-ethoxycarbonyl-5-nitr0-2-trifiuoromethylbenzimidazole, melting point 8587C.

27. 4,5-dichloro-l-phenoxycarbonyl-2- trifluoromethylbenzimidazole, melting point ll3ll4C.

28. 4-bromo-7-chlorol -ethoxycarbonyl-2- trifluoromethylbenzimidazole, melting point ll5-117C.

29. l-ethoxycarbonyl-5-iodo-2-trifluoromethylbenzimidazole, melting point 67C.

30. 4-bromo-l-ethoxycarbonyl-6-nitr0-2- trifluoromethylbenzimidazole, melting point l52l53C.

3 l 4,6-dibromo-1-isopropoxycarbonyl-2- trifluoromthylbenzimidazole, melting point l37138C.

32. 4-bromo-6-chloro-l-phenoxycarbonyl-2- triflioromethylbenzimidazole, melting point 33. 6-bromo-4-ehloro-l-ethoxycarbonyl-2- trifluoromethylbenzimidazole, off-white crystals, melting point 93-94C.

34. 6-bromo-4,5-dichloro-1-isopropoxycarbonyl-2- trifluoromethylbenzimidazole, off-white crystals, melting point l30-l 3 1C.

35. 4-bromo-6-chloro-l-isopropoxycarbonyl-Z- trifluoromethylbenzimidazole, melting point l42-l44C.

trifluoromethylbenzimidazole, 8082C.

trifluoromethylbenzimidazole, l l9l22C.

trifluoromethylbenzimidazole, 101C.

5-cyano-l-isopropoxycarbonyl-2- melting point 6-bromo-4,5-dichlorol -ethoxycarbonyl-2- melting point 5 ,6-dichlorol -ethoxycarbonyl-2- melting point 5 ,6-dichloro-1 -methoxycarbonyl-2- trifluoromethylbenzimidazole, melting point 141C.

40. 6-chloro-4-nitrol -ethoxycarbonyl-2- vtrifluoromethylbenzimidqzole, melting point 41. 4-chloro-6-iodo- 1 -2-trifluoromethylbenzimidazole, melting point 9395C.

42. 5 ,6-dichlorol -cyclohexyloxycarbonyl-2- trifluoromethylbenzimidazole, melting point 7980C.

43. 6-bromo4,5-dichlorol 2 '-chloroeth0xycarbonyl)-2-trifluoromethylbenzimidazole, melting point l35-l37C.

44. 6-chloro-4-nitro-l-decyloxycarbonyl-2- trifluoromethylbenzimidazole, melting point 58-59C.

45. 4,5-dichloro-l-methoxycarbonyl-2- trifluoromethylbenzimidazole, melting point lll-ll2C.

46. 4,5-dichloro-l-cyclohexyloxycarbonyl-2- trifluoromethylbenzimidazole, melting point 87-88C.

47. 4,5 ,6-trichlorol -cyclohexyloxycarbonyl-2- trifluoromethylbenzimidazole, melting point l14-1l5C.

48. 4,5-dichloro-l-hexyloxycarbonyl-Z- trifluoromethylbenzimidazole, melting point 62-63C.

49. 4,5,6-trichloro-l-alphanaphthyloxycarbonyl-2- trifluoromethylbenzimidazole, melting point ll76C.

50. 4,6-dichlorol -phenoxycarbonyl-2- trifluoromethylbenzimidazole, melting point ll5ll6C.

51. 4-bromo-5 ,6-dichlorol -ethoxycarbonyl-2- trifluoromethylbenzimidazole,, melting point 142l43C.

52. 4-bromo-5,6-dichloro-l-pentyloxycarbonyl-2- trifluoromethylbenzimidazole, melting point 93-95C.

53. 4-bromo- 5,6-dichl0ro-l-propyloxycarbonyl-Z- trifluoromethylbenzimidazole, melting point l23125C.

EXAMPLE 54 Suspensions of the compounds according to the invention were made up in aqueous acetone containing 5 percent of the active ingredient. These suspensions were diluted with aerated distilled water to give compositions containing l0, 3, l and 0.3 parts per million (ppm) of the active ingredient. milliliter aliquots of the composition were placed in screw-cap glass jars, 4.5 centimeters diameter by 8.5 centimeters high, which just filled them to the brim. Five young specimens of the bilharzia vector snail, Australorbis glabratus, were then placed in each vessel and a perforated lid screwed on to prevent them leaving the water. The temperature was maintained at 28C. After a 24 hour exposure period the snails were removed from the solutions of the compounds and placed in aerated distilled water for a further 48 hour recovery period before an assessment of mortality was made. The results obtained are summarized in the following table, each value being the average of three replications.

11 mortality after 72 hours I00 100 l00 I00 100 100 lOO 40 EXAMPLE 55 Mustard, linseed, buckwheat and sugarbeet were grown in John lnnes No. l potting compost in aluminum pans (18 X 9 X 4 cm.) When the plants had between two and five true leaves they were sprayed with a solution of each of the compounds identified below in aqueous acetone at rates corresponding to 160, 80, 40 and 20 ounces per acre. After seven days in a controlled environment room at 22C. with 14 hours per day illumination of 800 ft. candles and at 75-90 percent relative humidity, the plants were assessed visually for any herbicidal effect. The results are tabulated below; 100 indicates complete destruction of the plant; 0 indicates no herbicidal effect.

Rate of evaporated the discs were placed in 9 cm petri dishes and each infested with ten second instar larvae of the Cabbage-white butterfly (Pieris brassicae). With every compound complete kill of the larvae was obtained within 24 hours.

l-carbomethoxy-4,5 ,6-trichloro-Z-trifluoromethylbenzimidazole. l-carbisopropoxy-4,5 ,6-trichloro-2-trifluoromethylbenzimidazole.

l-carbophenoxy-4,5 ,6-trichloro-2-trifluoromethylbenzimidazole. l-carbophenyoxy-5-bromo-2-trifluoromethylbenzimidazole.

EXAMPLE 58 Nine centimeter diameter filter papers were treated with acetone solutions of l-carbophenoxy-6-chloro-4- nitro-2-trifluoromethyl benzimidazole and when the solvent had evaporated, were placed in crystallizing dishes (9 cm X 4 cm). The concentrations of the solutions were adjusted so that l milliliter aliquots deposited on the papers produced deposits equivalent to 30, I0 and 3mg/sq. meter.

Adult female houseflies (Musca domestica), lightly Herbicidal effect application, Buck- Sugar- Compound oz./aci'e Mustard Linseed wheat beet 1-carboethoxy-Z-trifluoromethyli,5,6(5,6,7)-trichlorobemmldazm us 100 1 v5 20 T5 100 100 60 l l-carbqisopropoxy-Z-trifluoromethyM,5,6(5,6,7)-trichl0r0- 3g 88 benrimidazole 4O 85 U0 20 J0 15 l-carbophenoxy-2-trifluoromethyl4,5,6(5,6,7)trichl0ro- 160 9 E 100 100 benzimidazole 80 100 100 4O 7 100 70 20 50 70 H5 35 l-carboniethoxy-2-trifluoromothyl4,5,6(5,6,7)-tri -hl0ro- Y 40 so 100 100 100 20 8O I00 75 160 100 100 100 1-carbophon0xy-2,5-bis-(iriiluoronmthyl)bcnznmdazolc t 20 100 100 100 100 2.5 at us 100 35 l-carbophenoxy-Z-trifluoromethy1-4-ch1oro-6-nitrobenzimi- J8 100 100 100 azole a a 20 I00 100 100 100 I 2.5 50 50 100 20 1-carh0phei1oxy-2-trifluoroinethyl-4-n1tro-G-chloroben21 160 100 100 100 100 midazolc 20 100 100 100 100 .5. 5 80 518 100 JO EXAMPLES 56 EXAMPLE 57 An acetone solution of each of the compounds indicated below was sprayed onto 7 cam discs of cabbage leaves so as to give coatings of 3 micrograms of active ingredient per square centimeter. After the solvent had anaesthetized with carbon dioxide were then introduced into the dishes and a glass lid placed over each. When examined after 24 hours, all treatments were found to have given a complete kill of the insects.

EXAMPLE 59 Filter papers were treated with aqueous sugar solutions containing the sodium salt of the substituted benzimidazole indicated below, so as to give a deposit of the active ingredient of 10 mg/sq.meter.

Adult houseflies (Musca domestica) were transferred to cages containing this filter paper on the floor, and left for 24 hours, and mortality observed. In each case 100 percent mortality was obtained. The papers were stored in the open and at intervals the papers were tested again, to determine the number of days storage required for the mortality to fall at 50 percent. This persistence time in days is given in the table below.

l-carbophenoxy-6-chloro-4-nitro over 57 Z-trifluoromethyl benzimidazole l l 12 1carboisopr p xy Over 57 fected with cucumber mildew, Erysiphe ("'flwwmethyl) benzlm'damle cichoracearum, as a source of inoculum.

After 14 days, incubation the treatments were found EXAMPLE 60 to give 98, 91 and 72 percent protection respectively.

5 The compounds indicated below: EXAMPLE 62 An aqueous acetone suspension of l-carbophenoxy- Cmnlmunds 5 -iodo-2-trifluoromethylbenzimidazole containing 1'carbomethoxy'4si6'mchloro2' 2,000 p.p.m. wt./volume together with 500 p.p.m. of a trifluoromethylbenzimidazolewetting agent (Lissapol NX) were sprayed on young 1carboethoXy-4,5v6'tl'ichlom'z'tl'ifluoromethyl' french bean plants (Phaseolus vr lgaris) having two benzimidazolet fully expanded leaves. 24 hours after treatment the p y' y plants were dusted with spores of the beam rust, Urobenlimidalole l5 myces phaseoli. After days incubation in a controlled ar 0ph xyu t y environment room at 16C the pla nts were examined benzimidazole when it was found that the treatment had given 69 per- 5. 1-carbophenoxy-6-chloro-4-nitro-2- cent protection as compared with untreated controls.

trifluoromethylbenzimidazole. 6. 1-carboisopropoxy-6-ch1oro-4-nitro-2- 20 EXAMPLE 63 r fl r m hyl benlimidalole- A 1 percent solution of l-carboisopropoxy-6-chloro- 7. 1 -carbophenoxy-4-chl0r0-6-nitr -2- 4-nitro-2-trifluoromethylbenzimidaizole in trifluoromethylbenzimidazole. polyethylene glycol (Carbowax 400) was added to a 8. 1-carbopropoxy-4,5,6-trichloro-2-trifluoromethyl dextrose nutrient broth in quantities sufficient to give benzimidazole. 1,000, 200 and 40 ppm. w./volume of media. 8 cc were incorporated into the nutrient medium known as aliquots of the treated media were placed in test tubes potato-dextrose agar in the molten state at a rate s ffiand 0.2 mls. of a concentrated inoculum of the tomato cient to produce a final concentration of parts per Wilt bacterium, coryneb'acleriu'fl michiganeme added million weight/volume w/v) f the medium. to them. After 7 days incubation at 25C the broth The liquid was poured into petri dishes and the cooled 30 Specimens were exammed for slgnsiof bacterial growthculture plates inoculated with mycelial plugs (6 mm. N0 growthwas found in tubes'treated with the diameter) of a selection from the following species: Pound at levels The process of this example was repeated replacing Lem" species the 1-carboisopropoxyi-6-chloro-4-nitro-2- A. Phytophlhora palmivora trlfluoromethylbenzimidazole by 5-bromo-1-car- 2- 5 '5"??? golani bophenoxy-Z-trifluoromethylbenzimidazole. No

Z van when growth was found at the 1,000 and 200 p.p.m. levels of E. Verticillium albo-alrum treatment. i

F. Fomes annosus G. Aspergillus niger 40 EXAMPLE 64 H. Cladosparium herbarum I. Penicillium digimrum A 1% solution of 1-carbophenoxy-5,6-dichloro-2- trifluoromethylbenzimidazole in polyethylene glycol The plates were cultured for 7 days at 20C when the (Carbowax 400) was added to a dextrose nutrient colony diameters were me u a c mp with broth in quantities sufficient to give 1,000, 100 and 40 the untreated controls. In the following table the reducp.p.m. w/v of media. 8 cc aliquots of the treated media tion in fungal growth is recorded; a dash indicates no were placed in test tubes and 0 2 mls of a concentrated test. inoculum of Xanthomonas malvacearum (black arm RE-15061007}! iii WF o fixL GROWTH Species A B o 1) E F G H 1 Compound:

%... Over 50%... Over 50 Over 50%. Over 50%. OVCI'50% do do do (io do do do. do Over-50%." Over 50%... Over 50% .do... .(lo. (lo do Do. do H... (l() (l0 (lo 1J0. 7 Do. Oval-50% H0. 8 ()vorfiOQL. )vi 1'5ll}{,, 0vur5ll},,

EXAMPLE 61 disease of cotton) added to them. After 7 days incobuation at 25C the broth specimens were examined for q o 866K011? suspensions of l-carbomethoxysigns of bacterial growth. No growth was found in tubes 4,5,6-tl'lchlow-2'tflfluofomelhylbenzimidazole treated with the compound at all levels of concentrataining 50, 250and 125 parts per million wt./vo1ume ti n, together with 500 parts per million of a suitable wetting Th ro ss of this example was repeated replacing agent (LISSaPOI were p y t0 cucumber 65 the 1-carbophenoxy-5,6,-dichlorQ-Z-trifluoromethylplants with two fully expanded true leaves. The treated benzimidazole by l-carboisopropoxy-6-chloro-4-nitroplants were then placed in a controlled environment 2-trifluoromethylbenzimidazole. No growth was found chamber together with a number of plants heavily inat the 200 p.p.m. level of treatment.

EXAMPLE 65 According to one embodiment of the invention the physiologically active composition also contains another active ingredient such as a herbicide, for example 2-methyl-4-chlorophenoxyacetic acid, 2,4- dichlorophenoxyacetic acid or a triazine; an insecticide, for example DDT or sevin; or a fungicide, for example a dithiocarbamate.

The following emulsifiable oil formulations were made up using the commercially available emulsifying agents as specified 5 Formulation A l-carbophenoxy-2,S-bis (trifluoromethyl)benzimidazole. 20 g.

Arylan CA (Calcium salt of dodecylbenzene EXAMPLE 67 sulphonic acid) 3.45 g. PE5 l t ri g camllgnsate French beans (Phaseolus vulgaris) plants were ma mo e nem s e y e y 115 sprayed with solutions containing 1,000 parts million of pffi 83 2 g gig pr f afigsg each of the compounds identified below and 500 parts e O gfli g y s o y L per million of the non-ionic wetting agent Lissapol NX Solvent naphtha to make 100 ml. 15 in aqueous acetone.

At intervals of l, 3, 7, l0, l4, 17, 21 and 24 days Formulatlon B after spraying, 2 cm. diameter leaf discs were cut and each infested with 25 adult red spider mites ifiggfg'ggfigggf: 22 g Tetranychus telarius). The leaf discs were kept on Arylan CA 3.08 g. moist filter paper for 48 hours and after this time the Sapogenat T 110 1.06 g. sapogenan 500 2m g percentage of spider mites dead was observed. Results Petroleum Naphtha to make 100 ml. were as follows:

5,6-Dichloro-l-phenoxycarbonyl-2-trifluoromethyl v o mula on C benzimidazole, more than 50 percent dead with infestation 24 days after spraying. l-carbo henoxy-2-triiluoromethyl-4-chloro-6- 4-Bromo-6-chloro-l -ethoxycarbobyl-2- g' fi' i 3681? trifluoromethylbenzimidazole, more than 50% SapogenatT 110 1.75 g. dead with infestation 10 days after spraying. SapogenatT 500 i 2.24 g. Petroleum Naphtha to make 100 ml 6 Bromo 4 chloro l ethoxycarbonyl 2 trifu loi'omethylbenzimidazole, more than SOpercent Formulation D dead with infestation 2ft days after spraying.

6-Bromo-4,5-dichloro-l-isopropoxycarbonyl-2- 1 ca,b9eqmy 2 mfluo,memy1 5 bmmo trifluoromethylbenzimidazole, more than 50 perbenzimidazole I s- 5 cent dead with infestation 17 days after spraying. lskrylanvca T l g. apogenat 10 i g. Petroleum Naphtha to make 100 ml. EXAMPLE 68 French beans (Phaseolus vulgaris) plants were r f formulatlons water sprayed with solutions containing 1,000 parts million of agitation, to make emulsions containing 0.l33 lb. ac- 40 each of the compounds identified below and 500 parts tive ingredient in 1 gallon and sprayed at rates of 30 per million of the non-ionic wetting agent Lissapol N X gallons/acre (4 lb. active ingredient/acre) on to seed in aqueous acetone.

ans containin the weed seedlin s s ecified in the tale, grown in th e greenhouse to 3 4 (16 leaves. After4 At Intervals of 2] and 24 days days the percentage of the leaf area killed was estimated visually. Weed species :ormulations after spraying, 2 cm. diameter leaf discs were cut and each infested with 10 female adult red spider mites (Tetranychus telarius) and placed on moist filter paper. The adult mites were left on the discs for 24 hours, durganicum 57 6 8. ing which time each laid about 10 eggs (if the adult it- Setaria 97 o self did not die). The adults were then removed and the aickweed 94 38 f3 9,: percentage emergence from the eggs after 7 days was Dock 96 4 53 96 observed. Results were as follows: 3333 33 :3 :3 3g 5 ,6Dichlor0- l -phenoxycarbonyl-2-trifluoromethylbenzimidazole, less than percent emergence 55 with infestation 24 days after spraying. EXAMPLE 66 4-Bromo-6-chloro-l -ethoxycarbonyl-2- trifluoromethylbenzimidazole, less than 50 percent emergence with infestation 7 days after spraying. 4,6-Dibromo-l-isopropoiiycarbonyl-2- trifluoromethylbenzimidazole, less than 50 per- A wettable powder was made up as follows:

25 parts of l-carboethoxy-Z-trifluoromethyl-S- bromo-benzimidazole 2 parts of the sulphated dodecylalcohol-ethylene oxide condensation product commercially availabi as HOE 52/26g cent emergence with infestation 10 days after 5 parts of the sodium sulphate lye commercially p y availabl as Wafe 6-Bromo-4-chloro-l-ethoxycarbonyl-2- 68 parts of chinaclay. trifluoromethylbenzimidazole, less than 50 per- This wettable powder was suitable for dispersion in cent emergence with infestation 10 days after water and spraying. spraying.

EXAMPLE 69 A wettable powder formulation was made up by grinding in a microniser the following ingredients:

5,6-Dichlorol-phenoxycarbonyl-Z- trifluoromethylbenzimidazole 25% The condensation roduct of ethylene oxide wi fatty alcohols,

known as Hoe 821268. 3% The sodium salt of the sulphonated cresol/urea/formaldehyde condensation product known as Dyapol pt 226% China clay EXAMPLE 70 The wettable powder prepared as in Example 3 was dispersed in water to give concentrations of 0.03 percent and 0.05 percent of 5,6-dichloro-l-phenoxycarbonyl-2-trifluoromethylbenzimidazole. These dispersions were sprayed onto 20 year old apple trees (var. Rome Beauty) in an orchard in South Africa one month before harvesting the apples at a rate of 2 gallons of spray liquid to each tree. Each treatment was replicated four times. Before spraying, and at intervals of 2 days and 7 days after spraying, a random sample of 40 leaves was taken from each tree treated and also from untreated controls and the percentage which were infected with red spider mites (Tetranychus telarius) was noted. The results (averaged for the four replicates of each treatment) are as follows:

Before 2 days after 7 days after raying s raymg 5 re in 0.5% compound 5%% f p li 0.03% compound 73% 8% 0% Control 68% 72% 93% EXAMPLE 7] French beans (Phaseolus vulgaris) plants were sprayed with solutions containing 1,000 parts per million of each of the compounds identified below and 500 parts per million of the non-ionic wetting agent Lissapol NX in aqueous acetone.

Atintervals of numbers of days after spraying 2 cm. diameter leaf discs were cut and each infested with 25 adult red spider mites (Tetranychus telarius). The leaf discs were kept on moist filter paper for 48 hours and after this time the percentage of spider mites dead was recorded. In the table below is given for each compound the number of days after spraying when test discs were cut and infested and more than 50 percent mortality of the mites was observed. 4-bromo-6-chloro-l-isopropoxycarbonyl-2- trifluoromethyl-benzimidazole 10 days,

benzimidazole 7 days, 6-chloro-4-nitro-l-ethoxycarbonyl-Z- trifluoromethylbenzimidazole 17 days, 4-chloro-6-iodo-l-ethoxycarbonyl-Z- trifluoromethylbenzimidazole 10 days, 5 ,6-dichloro-l -cyclohexyloxycarbobyl-2- trifluoromethylbenzimidazole 14 days,

6-bromo-4,5-dichloro- 1 2'-chloroethoxycarbonyl 2-trifluoromethylbenzimidazole 10 days, 4,5-dichlorol -methoxycarbonyl-2-trifluoromethylbenzimidazole 10 days, 4,5-dichloro-1-cyclohexyloxycarbonyl-2- trifluoromethylbenzimidazole 10 days, 4,5,6-trichloro-l-cyclohexyloxycarbonyl-2- trifluoromethylbenzimidazole 24 days, 4,5-dichloro-l-hexyloxycarbonyl2-trifluoromethylbenzimidazole 10 days, 4,5,6-trichloro-l-alphanaphthyloxycarbonyl-Z- trifluoromethylbenzimidazole 10 days, 4,6-dichlorol -phenoxycarbonyl#2-trifluoromethylbenzimidazole 10 days,

4-bromo-5 ,6-dichlorol -ethoxycarbonyl-2- trifluoromethylbenzimidazole 17 days, 4-bromo-5 ,6-dichloro-1-pentyloxycarbonyl-2- trifluoromethylbenzimidazole 10 days, 4-bromo-5 ,6-dichlorol -propyloxycarbonyl-2- trifluoromethylbenzimidazole 14 days,

6-chloro-4-nitro-l-decyloxycarbonyl-Z- trifluoromethylbenzimidazole 10 days, 6-chloro-4-nitro-1-isopropoxycarbonyl- 2trifluoromethylbenzimidazole 10 days, 4,5-dichloro-l -ethoxycarbonyl-Z-trifluoromethylbenzimidazole 7 days,

4 ,5 -dichlorol -isopropoxycarbonyl-2- trifluoromethylbenzimidazole 7 days,

5 -nitrol -isopropoxycarbonyl-2-trifluoromethylbenzimidazole 35 days, 5 4,6-dibromo-l -ethoxycarbonyl-2-trifluoromethylbenzimidazole 24 days,

4-bromo-6-chloro-1 -phenoxycarbonyl-2- trifluorobenzimidazole 10 days.

What is claimed is: l

l. A method for the control of acarida which comprises bringing into contact with an acarid an acaricidal composition which comprises an acaricidally effective amount of 5 ,6dichlorol -phenoxycarbonyl-2- trifluoromethylbenzimidazole in admixture with a compatible carrier.

2. A method according to claim 1 wherein the acaricidal composition is applied to plants which re subject to damage by acarida.

3. A method according to claim 1 wherein the acaricidal composition contains a wetting agent.

4. An acaricidal composition which comprises an acaricidally effective amount of 5,6-dichloro-lphenoxy-carbonyl -2-trifluoromethylbenzimidazole in admixture with a compatible carrier.

5. A composition according to claim 4 said composition containing a wetting agent.

i t i 4 r 

2. A method according to claim 1 wherein the acaricidal composition is applied to plants which re subject to damage by acarida.
 3. A method according to claim 1 wherein the acaricidal composition contains a wetting agent.
 4. An acaricidal composition which comprises an acaricidally effective amount of 5,6-dichloro-1-phenoxy-carbonyl -2-trifluoromethylbenzimidazole in admixture with a compatible carrier.
 5. A composition according to claim 4 said composition containing a wetting agent. 